CN111755726A - Preparation method of membrane electrode, membrane electrode and fuel cell - Google Patents
Preparation method of membrane electrode, membrane electrode and fuel cell Download PDFInfo
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- CN111755726A CN111755726A CN202010663130.9A CN202010663130A CN111755726A CN 111755726 A CN111755726 A CN 111755726A CN 202010663130 A CN202010663130 A CN 202010663130A CN 111755726 A CN111755726 A CN 111755726A
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention belongs to the technical field of fuel cells, and particularly relates to a membrane electrode preparation method S1, wherein an opening is formed in an inner frame part of a first frame membrane, and then the first frame membrane and a second frame membrane are pre-laminated to obtain a pre-laminated frame membrane; or, pre-laminating a first frame film and a second frame film, and then forming an opening along the inner frame part of the first frame film to obtain a pre-laminated frame film; the opening extends from the inner frame of the first frame film to the outer frame of the first frame film; s2, uncovering part of the first frame film along the opening, and embedding the proton exchange membrane into the pre-facing frame film; and S3, completely jointing the proton exchange membrane and the pre-butted frame membrane, and closing the opening to obtain the membrane electrode. Compared with the prior art, the invention does not need to respectively attach two side frame membranes on two sides of the proton exchange membrane, simplifies the preparation process of the membrane electrode and improves the alignment precision of the two side frame membranes.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a preparation method of a membrane electrode, a membrane electrode and a fuel cell.
Background
A Membrane Electrode Assembly (MEA), also known as a membrane electrode "three-in-one" or "five-in-one" assembly, is a core component of a Proton Exchange Membrane Fuel Cell (PEMFC), and is a place for energy conversion inside the fuel cell. The membrane electrode is responsible for multi-phase substance transmission (including liquid water, hydrogen, oxygen, proton and electron transmission) in the fuel cell and is responsible for converting the chemical energy of the fuel hydrogen into electric energy through electrochemical reaction. The performance and cost of the membrane electrode affects and even determines the performance, lifetime and cost of the PEMFC.
Currently, the preparation method of the membrane electrode includes the following steps: 1) preparing the proton exchange membrane and the frame membrane into sheet materials, and then laminating the sheet materials layer by layer according to corresponding position relation to prepare a sheet type membrane electrode; 2) the proton exchange membrane is used as a coil material supporting belt, catalyst layers are firstly manufactured on two sides of the proton exchange membrane, and then frame membranes are respectively compounded on the two sides. No matter which method is used, the frame films are required to be respectively attached to the two sides of the membrane electrode, namely, the frame films are attached at least twice and are affected by the attaching process, and the alignment deviation of the frame films on the two sides is easy to occur.
In view of the above, it is necessary to provide a method for preparing a membrane electrode to solve the above technical problems.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the preparation method of the membrane electrode is provided, two frame membranes do not need to be attached respectively, the preparation process is simplified, and the alignment precision of the two frame membranes is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of making a membrane electrode comprising the steps of:
s1, firstly, opening an opening in the inner frame part of the first frame film, and then pre-bonding the first frame film and the second frame film to obtain a pre-bonded frame film; or, pre-laminating the first frame film and the second frame film, and opening the inner frame part of the first frame film to obtain a pre-laminated frame film; the opening extends from the inner frame of the first frame film to the outer frame of the first frame film;
s2, uncovering part of the first frame film along the opening, and embedding the proton exchange membrane into the pre-facing frame film;
and S3, completely jointing the proton exchange membrane and the pre-butted frame membrane, and closing the opening to obtain the membrane electrode.
As an improvement of the preparation method of the membrane electrode of the present invention, in S2, catalyst layers are combined on both sides of the proton exchange membrane, and the catalyst layers and the pre-facing frame membrane are partially overlapped. The catalyst layer has the fractional overlap with the frame membrane, so counterpoint makes the marginal part of catalyst layer get up by the frame membrane cladding respectively, plays the guard action to comparatively fragile catalyst layer. In addition, the structure can prevent the proton exchange membrane from being oxidized.
As an improvement of the preparation method of the membrane electrode of the present invention, in S2, both sides of the proton exchange membrane are not composited with a catalyst layer; in S3, after the proton exchange membrane and the frame membrane are completely bonded, the catalyst layers are respectively laminated on both sides of the proton exchange membrane. So, the catalyst layer with in advance to the laminating of the inward flange of welt frame membrane and not overlapping, because the catalyst layer can't play the catalytic action in fact with the part of overlapping to the welt frame membrane in advance, so set up the waste that can avoid the catalyst layer.
As an improvement of the preparation method of the membrane electrode of the present invention, in S2, a first catalyst layer is composited on one surface of the proton exchange membrane; in S3, the proton exchange membrane and the frame membrane are completely bonded, and then a second catalyst layer is combined on the other side of the proton exchange membrane. So set up, the catalyst layer has partial overlap with in advance to the frame membrane one side of welting, and the one side does not overlap, can practice thrift partly unable catalyst layer that plays the catalytic effect, can avoid proton exchange membrane to take place the oxidation again.
As an improvement of the method for preparing the membrane electrode of the present invention, the method for pre-laminating the first frame membrane and the second frame membrane includes any one of ultraviolet irradiation, heating, pressurization or magnetic field treatment. The method of pre-laminating the first frame film and the second frame film may be any one known in the art, and is preferably any one of ultraviolet irradiation, heating, pressure, and magnetic field treatment. In S1, when the first frame film and the second frame film are pre-bonded, the portion of the proton exchange membrane that is reserved is not bonded; after the proton exchange membrane is embedded, the pre-butted frame membrane and the proton exchange membrane are completely jointed.
As an improvement of the preparation method of the membrane electrode, the method for completely jointing the proton exchange membrane and the pre-jointing frame membrane comprises any one of ultraviolet irradiation, heating, pressurization or magnetic field treatment. The proton exchange membrane and the frame membrane to be adhered can be adhered completely by any method known in the art, preferably any one of ultraviolet irradiation, heating, pressurization or magnetic field treatment.
As an improvement of the membrane electrode manufacturing method of the present invention, the opening extends toward the outer frame along a reverse extension of a diagonal line of the inner frame. The number of the openings can be only four, the four openings respectively extend towards the outer frame along the opposite direction of the diagonal line of the first edge inner frame, and part of the first edge film is lifted along the openings, so that the proton exchange film or the proton exchange film compounded with the catalyst layer can be conveniently embedded. It should be noted that the end of the opening must not extend beyond the sealing area of the sealing ring, which would affect the sealing effect.
As an improvement of the membrane electrode manufacturing method of the present invention, the opening extends toward the outer frame along a reverse extension line of the inner frame. The opening is only required to be convenient for uncovering part of the first frame membrane and can be embedded into the proton exchange membrane or the proton exchange membrane compounded with the catalyst layer.
As an improvement of the preparation method of the membrane electrode, one surface of the pre-butted frame membrane facing the proton exchange membrane is also provided with a binder for binding the proton exchange membrane. The adhesive comprises pressure-sensitive adhesive, ultraviolet curing adhesive or hot melt adhesive. Pressure-sensitive adhesives, including but not limited to solvent-based pressure-sensitive adhesives, emulsion-type pressure-sensitive adhesives, hot-melt pressure-sensitive adhesives and radiation-curable pressure-sensitive adhesives, can be bonded by flat pressing or rolling after alignment, and realize complete bonding with the frame film of the facing frame and closing of the opening. The ultraviolet curing glue is an adhesive which can be cured only by ultraviolet irradiation, and after alignment, the ultraviolet irradiation is carried out on the part of the ultraviolet curing glue, so that complete attachment of the frame attaching film and closing of the opening can be realized. The hot melt adhesive is a thermoplastic elastomer or an EVA (ethylene vinyl acetate) adhesive film which does not have an adhesive effect at normal temperature, and after alignment and hot-pressing lamination, the hot melt adhesive can be fused and bonded, so that complete lamination of the laminated frame film and closing of the opening are realized.
As an improvement of the preparation method of the membrane electrode, the proton exchange membrane comprises a perfluorinated sulfonic acid resin proton exchange membrane, a sulfonated polyphenyl quinoxaline proton exchange membrane, a sulfonated poly-diphenol proton exchange membrane, a polybenzimidazole proton exchange membrane, a polyether-ether-ketone proton exchange membrane, a sulfonated polysulfone proton exchange membrane, a sulfonated polyether sulfone proton exchange membrane or a porous PTFE composite proton exchange membrane deposited with perfluorinated sulfonic acid resin.
As an improvement of the preparation method of the membrane electrode, the catalyst layer comprises a first catalyst layer and a second catalyst layer, the first catalyst layer and the second catalyst layer both contain noble metal catalysts or carbon-supported noble metal catalysts, wherein the noble metal loading is 0.01-1 mg/cm2The noble metal is at least one of Pt, Ru, Ir, Au, Ag and Pd, or the noble metal is binary or above alloy formed by at least one of Pt, Ru, Ir, Au, Ag and Pd and Co, Ni or Mn, and the thickness of the first catalyst layer and the second catalyst layer is 0.5-100 μm.
As an improvement of the preparation method of the membrane electrode, the first frame film and the second frame film comprise one of a PET film, a PE film, a PP film, a PI film and a PEN film or a composite film formed by at least two of the PET film, the PE film, the PP film, the PI film and the PEN film, and the thickness of the first frame film and the second frame film is 10-500 μm.
The second purpose of the invention is: there is provided a membrane electrode prepared by the method of any preceding paragraph.
The third purpose of the invention is that: there is provided a fuel cell comprising a membrane electrode as hereinbefore described.
Compared with the prior art, the invention at least has the following beneficial effects: the invention provides a preparation method of a membrane electrode, which comprises the following steps: s1, firstly, opening an opening in the inner frame part of the first frame film, and then pre-bonding the first frame film and the second frame film to obtain a pre-bonded frame film; or, pre-laminating a first frame film and a second frame film, and then forming an opening along the inner frame part of the first frame film to obtain a pre-laminated frame film; the opening extends from the inner frame of the first frame film to the outer frame of the first frame film; s2, uncovering part of the first frame film along the opening, and embedding the proton exchange membrane into the pre-facing frame film; and S3, completely jointing the proton exchange membrane and the pre-butted frame membrane, and closing the opening to obtain the membrane electrode. The invention firstly pastes the two frame films in advance, wherein at least one frame film is provided with a closable opening, and the two frame films are completely pasted and the opening is closed after the frame film is embedded into the proton exchange membrane, so that the pasting of the two frame films and the proton exchange membrane can be realized. Compared with the prior art, the invention does not need to respectively attach the frame membranes to the two sides of the proton exchange membrane twice, simplifies the preparation process of the membrane electrode and improves the alignment precision of the frame membranes on the two sides.
Drawings
Fig. 1 is a schematic view of the structure of the membrane electrode in example 1.
Fig. 2 is a sectional view of the membrane electrode in example 1.
Fig. 3 is a schematic view of the structure of the membrane electrode in example 2.
Fig. 4 is a sectional view of the membrane electrode in example 2.
Wherein: the catalyst comprises a proton exchange membrane 1, a catalyst layer 2, a first catalyst layer 21, a second catalyst layer 22, a first frame membrane 31, a second frame membrane 32, an opening 4 and a sealing ring 5.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and the accompanying drawings, but the embodiments of the invention are not limited thereto.
Example 1
As shown in fig. 1-2, the present embodiment provides a membrane electrode, and the preparation method thereof includes the following steps:
s1, firstly, opening an opening 4 in the inner frame part of the first frame film 31, and then pre-bonding the first frame film 31 and the second frame film 32 to obtain a pre-bonded frame film; the opening 4 extends along the inner frame of the first frame film 31 to the outer frame of the first frame film 31;
s2, uncovering part of the first frame film 31 along the opening 4, and embedding the proton exchange membrane 1 into the pre-facing frame film;
and S3, completely jointing the proton exchange membrane 1 and the pre-butted frame membrane, and closing the opening 4 to obtain the membrane electrode.
Further, in S2, both surfaces of the proton exchange membrane 1 are not combined with the catalyst layer 2; in S3, the proton exchange membrane 1 and the frame membrane are completely bonded, and then the catalyst layers 2 are respectively laminated on both sides of the proton exchange membrane 1. So, catalyst layer 2 and the laminating of the inward flange to the frame membrane of facing in advance and do not overlap, because catalyst layer 2 and the part of overlapping to the frame membrane of facing in advance can't play the catalytic action in fact, so set up the waste that can avoid catalyst layer 2.
Further, the method of pre-laminating the first frame film 31 and the second frame film 32 includes any one of ultraviolet irradiation, heating, pressurization, or magnetic field treatment. The method of pre-laminating the first frame film 31 and the second frame film 32 may be any one known in the art, and is preferably any one of ultraviolet irradiation, heating, pressure, and magnetic field treatment. In S1, when the first frame film 31 and the second frame film 32 are pre-bonded, the portion of the proton exchange membrane 1 that is reserved is not bonded; after the proton exchange membrane 1 is embedded, the pre-facing frame membrane and the proton exchange membrane 1 are completely attached.
Further, the method for completely attaching the proton exchange membrane 1 and the frame membrane to be attached includes any one of ultraviolet irradiation, heating, pressurization or magnetic field treatment. The proton exchange membrane 1 and the frame membrane to be bonded may be formed by any method known in the art, and preferably by any one of ultraviolet irradiation, heating, pressurization, or magnetic field treatment.
Further, the opening 4 extends toward the outer frame along a reverse extension of a diagonal line of the inner frame. The number of the openings 4 can be only four, the four openings 4 respectively extend towards the outer frame along the opposite direction of the diagonal line of the first edge inner frame, and part of the first edge frame film 31 is lifted along the openings 4, so that the proton exchange membrane 1 or the proton exchange membrane 1 compounded with the catalyst layer 2 can be conveniently embedded. It should be noted that the end of the opening 4 must not exceed the sealing area of the sealing ring 5, which would affect the sealing effect.
Further, the proton exchange membrane 1 comprises a perfluor sulfonic acid resin proton exchange membrane, a sulfonated polyphenyl quinoxaline proton exchange membrane, a sulfonated poly diphenol proton exchange membrane, a polybenzimidazole proton exchange membrane, a polyether-ether-ketone proton exchange membrane, a sulfonated polysulfone proton exchange membrane, a sulfonated polyether sulfone proton exchange membrane or a porous PTFE composite proton exchange membrane deposited with perfluor sulfonic acid resin.
Further, the catalyst layer 2 comprises a first catalyst layer 21 and a second catalyst layer 22, the first catalyst layer 21 and the second catalyst layer 22 both contain noble metal catalysts or carbon-supported noble metal catalysts, wherein the noble metal loading is 0.01-1 mg/cm2The noble metal is at least one of Pt, Ru, Ir, Au, Ag and Pd, or the noble metal is binary or higher alloy formed by at least one of Pt, Ru, Ir, Au, Ag and Pd and Co, Ni or Mn, and the thickness of the first catalyst layer 21 and the second catalyst layer 22 is 0.5-100 μm.
Further, the first frame film 31 and the second frame film 32 include, but are not limited to, any one of a PET film, a PE film, a PP film, a PI film, and a PEN film, or a composite film composed of at least two of the foregoing films, and the first frame film 31 and the second frame film 32 have a thickness of 10 to 500 μm.
Example 2
As shown in fig. 3 to 4, the present embodiment provides a membrane electrode, which is different from embodiment 1 in the preparation method,
in S1, the first frame film 31 and the second frame film 32 are pre-laminated, and the inner frame portion of the first frame film 31 is provided with the opening 4, so as to obtain a pre-laminated frame film;
in S2, the catalyst layer 2 is laminated on both surfaces of the proton exchange membrane 1, and the catalyst layer 2 and the frame membrane are partially overlapped. The catalyst layer 2 and the frame film are overlapped in a small part, so that the edge parts of the catalyst layer 2 are respectively covered by the frame film by alignment, and the fragile catalyst layer 2 is protected. Besides, the structure can prevent the proton exchange membrane 1 from being oxidized.
Further, the opening 4 extends toward the outer frame along a reverse extension line of the inner frame. The opening 4 is only required to be capable of being embedded into the proton exchange membrane 1 or the proton exchange membrane 1 combined with the catalyst layer 2 so as to uncover a part of the first frame membrane 31.
The rest is the same as embodiment 1, and the description is omitted here.
Example 3
This example provides a membrane electrode, which is prepared by a method different from that of example 1,
in S2, a first catalyst layer 21 is combined on one surface of the proton exchange membrane 1; in S3, the proton exchange membrane 1 is completely bonded to the frame membrane, and then the second catalyst layer 22 is laminated on the other side of the proton exchange membrane 1. So set up, can practice thrift a part catalyst layer 2 that can't play the catalytic effect, can avoid proton exchange membrane 1 to take place the oxidation again.
The rest is the same as embodiment 1, and the description is omitted here.
Example 4
The present embodiment provides a fuel cell comprising the membrane electrode of embodiment 1, a frame member surrounding the membrane electrode, and a pair of separators with the frame member and the membrane electrode sandwiched therebetween.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. A preparation method of a membrane electrode is characterized by comprising the following steps:
s1, firstly, opening an opening in the inner frame part of the first frame film, and then pre-bonding the first frame film and the second frame film to obtain a pre-bonded frame film; or, pre-laminating the first frame film and the second frame film, and opening the inner frame part of the first frame film to obtain a pre-laminated frame film; the opening extends from the inner frame of the first frame film to the outer frame of the first frame film;
s2, uncovering part of the first frame film along the opening, and embedding the proton exchange membrane into the pre-facing frame film;
and S3, completely jointing the proton exchange membrane and the pre-butted frame membrane, and closing the opening to obtain the membrane electrode.
2. The membrane electrode assembly manufacturing method according to claim 1, wherein in S2, both surfaces of the proton exchange membrane are combined with catalyst layers, and the catalyst layers and the pre-facing frame membrane are partially overlapped.
3. The membrane electrode production method according to claim 1, wherein in S2, neither side of the proton exchange membrane is compounded with a catalyst layer; in S3, after the proton exchange membrane and the frame membrane are completely bonded, the catalyst layers are respectively laminated on both sides of the proton exchange membrane.
4. The membrane electrode assembly production method according to claim 1, wherein in S2, a first catalyst layer is laminated on one side of the proton exchange membrane; in S3, the proton exchange membrane and the frame membrane are completely bonded, and then a second catalyst layer is combined on the other side of the proton exchange membrane.
5. The method of manufacturing a membrane electrode according to claim 1, wherein the method of pre-laminating the first frame film and the second frame film includes any one of ultraviolet irradiation, heating, pressurization, or magnetic field treatment.
6. The method of manufacturing a membrane electrode according to claim 1, wherein the method of integrally bonding the proton exchange membrane and the frame pre-bonding membrane comprises any one of ultraviolet irradiation, heating, pressurization, or magnetic field treatment.
7. The method of manufacturing a membrane electrode assembly according to claim 1, wherein the opening extends toward the outer frame along a reverse extension of a diagonal line of the inner frame.
8. The method of manufacturing a membrane electrode according to claim 1, wherein the first frame film and the second frame film comprise any one of a PET film, a PE film, a PP film, a PI film, and a PEN film, or a composite film of at least two thereof, and the thickness of the first frame film and the second frame film is 10 to 500 μm.
9. A membrane electrode, characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. A fuel cell comprising the membrane electrode of claim 9.
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| CN202010663130.9A CN111755726B (en) | 2020-07-10 | 2020-07-10 | Membrane electrode preparation method, membrane electrode and fuel cell |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112886041A (en) * | 2021-01-15 | 2021-06-01 | 苏州泰仑电子材料有限公司 | Membrane electrode preparation system of fuel cell |
| CN112909293A (en) * | 2021-01-15 | 2021-06-04 | 苏州泰仑电子材料有限公司 | Proton exchange membrane composite sealing structure, membrane electrode and fuel cell |
| CN112909289A (en) * | 2021-01-15 | 2021-06-04 | 苏州泰仑电子材料有限公司 | Preparation method and system of proton exchange sealing membrane of fuel cell |
| CN113809373A (en) * | 2021-08-06 | 2021-12-17 | 无锡先导智能装备股份有限公司 | Seven-in-one forming equipment |
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